Aromatic/acrylate tackifier resin and acrylic polymer blends

ABSTRACT

An adhesive composition comprising at least one tackifier resin and at least one acrylic polymer is provided wherein the tackifier resin comprises monomer repeating units from at least one aromatic monomer and at least one acrylate monomer; and wherein the tackifier resin has a low residual monomer concentration. Processes to produce the adhesive composition is also provided.

FIELD OF THE INVENTION

This invention is related to the field of tackifier resin and acrylicpolymer blends. More specifically, this invention is related to thefield of tackifier resin and acrylic polymer blends wherein saidtackifier resin comprises repeating units from at least one aromaticmonomer and at least one acrylic monomer; and wherein the tackifierresin has a low residual monomer concentration. The invention is alsorelated to the field of processes to produce these tackifier resin andacrylic polymer blends.

BACKGROUND OF THE INVENTION

Tackifying resins are often used to modify various acrylic polymers toproduce adhesive compositions. Traditional tackifier resins include, forexample, rosins, rosin esters, colophonium-based resins, C₅ and C₉ basedhydrocarbon resins, terpene-based resins, coumarone and indene-basedresins, and phenolic resins. These tackifiers are used to produce, forexample, pressure-sensitive adhesives and hot-melt adhesives.

Many of these commercial tackifiers cannot be used in certainapplications. For example, in medical applications, some tackifierscannot be utilized due to skin sensitivity concerns. The medicaladhesive industry has a perception that rosins and rosin esters cancause skin sensitivity, therefore, rosins and rosins esters may not beused in this application.

In addition, tackifier resins used in many adhesive applications need tobe clear and to not cause fogging. Also, tackifier resins may also needto not inhibit the breathability of an adhesive composition as indicatedby the moisture vapor transport rate of the adhesive composition afterthe tackifier resin is added.

Therefore, there is a need in the adhesive industry for new tackifier.resins that can modify acrylic polymers and provide these properties.

SUMMARY OF THE INVENTION

In accordance with one embodiment of this invention, an adhesivecomposition is provided comprising at least one tackifier resin and atleast one acrylic polymer wherein the tackifier resin comprises monomerunits from at least one aromatic monomer and at least one acrylatemonomer; and wherein the tackifier resin has a low residual monomerconcentration.

In accordance with another embodiment of this invention, a process isprovided to produce the adhesive composition. The process comprisesproviding the tackifier resin and at least one acrylic polymer toproduce the adhesive composition.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 shows the relationship of Total UV to UV-C dose.

DETAILED DESCRIPTION

In an embodiment of this invention, an adhesive composition is providedcomprising at least one tackifier resin and at least one acrylicpolymer; wherein the tackifier resin comprises monomer repeating unitsfrom at least one aromatic monomer and at least one acrylate monomer;and wherein the tackifier resin has a low residual monomerconcentration.

The aromatic monomer can be any aromatic monomer known in the artcapable of polymerizing with at least one acrylate monomer to producethe tackifier resin. The term “aromatic monomer” means a monomercontaining at least one group of unsaturated cyclic hydrocarbonscontaining one or more rings. Examples of aromatic monomers include, butare not limited to, olefinic substituted aromatics, such as, styrene,alpha-methyl styrene, vinyl toluene, indene, methylindenes,divinylbenzene, dicyclopentadiene, and methyl-dicyclopentadiene. Mostpreferably, the aromatic monomer is styrene. The aromatic monomer can beadded to a reactor zone in the polymerization process as a single typeof monomer or a mixture and can be added in varying amounts and atvarying addition times during the polymerization.

The acrylate monomer is any acrylate monomer known in the art capable ofpolymerizing with the aromatic monomer. The acrylate monomer can beadded to a reactor zone in the polymerization process as a single typeof monomer or as a mixture and can be added in varying amounts and atvarying addition times during the polymerization.

In one embodiment, the acrylate monomer has the general formula:R₁—CH═CR₂—COOR₃wherein R₁ is selected from the group consisting of hydrogen, aliphaticgroups, and aromatic groups; wherein R₂ is selected from the groupconsisting of hydrogen, aliphatic groups, and aromatic groups; andwherein R₃ is selected from the group consisting of hydrogen, aliphaticgroups, aromatic groups. The term “aliphatic” is defined as a straightor branched chain arrangement of constituent carbon atoms and includes,but is not limited to, alkanes, alkenes, alkadienes, and alkynes. Thealiphatic groups can contain functional groups, such as, but not limitedto, hydroxyl, cycloaliphatic, acid, epoxide, amide, acrylonitril andacrylate. Preferably, the aliphatic group has 1 to about 20 carbonatoms, more preferably, from 1 to 12. The term “aromatic group” means atleast one group of unsaturated cyclic hydrocarbons containing one ormore rings. Aromatic groups can be selected from the group consisting ofboth unsubstituted and substituted aromatic groups having constituentswith up to about 6 carbon atoms. Preferably, the aromatic group hasabout 6 to about 20 carbon atoms. The aromatic groups can containfunctional groups, such as, but not limited to, hydroxyl,cycloaliphatic, acid, epoxide, amide, acrylonitril and acrylate. In somecases, these functional groups can lead to an acrylate monomer that hasmore than one reactive site for polymerization or other reactions.

In one embodiment, both R₁ and R₂ of the acrylate monomer are hydrogen.When the acrylate monomer is a methacrylic compound, R₂ is a CH₃ group.

For acid functionality monomers, R₃ is often hydrogen, such as, acrylicacid and methacrylic acid. The acid functionality monomers can also bedifunctional components such as, for example, maleic acid, fumaric acidor can be the anhydride forms of these components.

In another embodiment, the functional group is often found in the R₃group. Suitable examples are hydroxyethylacrylate, glycidylmethacrylate,and 1,3-butanediol dimethylacrylate.

Examples of acrylate monomers include, but are not limited to, methylacrylate, acrylic acid, methacrylic acid, methyl methacrylate, ethylacrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate,isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexylmethacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, n-heptylacrylate, n-heptyl methacrylate, 2-methylheptyl(meth)acrylate, octylacrylate, octyl methacrylate, isooctyl(meth)acrylate,n-nonyl(meth)acrylate, iso-nonyl(meth)acrylate, decyl(meth)acrylate,isodecyl acrylate, isodecyl methacrylate, dodecyl(meth)acrylate,isobornyl(meth)acrylate, lauryl methacrylate, lauryl acrylate, tridecylacrylate, tridecyl methacrylate, stearyl acrylate, stearyl methacrylate,glycidyl methacrylate, alkyl crotonates, vinyl acetate, di-n-butylmaleate, di-octylmaleate, acetoacetoxyethyl methacrylate,acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate,acetoacetoxypropyl acrylate, diacetone acrylamide, acrylamide,methacrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, allylmethacrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfurylacrylate, cyclohexyl methacrylate, cyclohexyl acrylate, n-hexylacrylate, n-hexyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethylmethacrylate, isodecyl methacrylate, isodecyl acrylate, 2-methoxyacrylate, 2-methoxy methacrylate, 2-(2-ethoxyethoxy) ethylacrylate,2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, isobornylacrylate, isobornyl methacrylate, caprolactone acrylate, caprolactonemethacrylate, polypropyleneglycol monoacrylate, polypropyleneglycolmonomethacrylate, poyethyleneglycol(400)acrylate,polypropyleneglycol(400)methacrylate, benzyl acrylate, benzylmethacrylate, sodium 1-allyloxy-2-hydroylpropyl sulfonate,acrylonitrile, and the like.

Acrylate monomers are described in “The Brandon Worldwide MonomerReference Guide and Sourcebook” Second Edition, 1992, BrandonAssociates, Merrimack, N.H.; and in “Polymers and Monomers”, the1996–1997 Catalog from Polyscience, Inc., Warrington, Pa.

Two or more of the acrylate monomers may be used in combination.Preferably, the acrylate monomer has up to about 20 carbon atoms, suchas, but not limited to, acrylic acid, 2-ethylhexyl acrylate, methylmethacrylate, methyl acrylate, acrylic acid, methacrylic acid, methylmethacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butylmethacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexylacrylate, n-hexyl methacrylate, ethylhexyl acrylate, ethylhexylmethacrylate, n-heptyl acrylate, n-heptyl methacrylate,2-methylheptyl(meth)acrylate, octyl acrylate, octyl methacrylate,isooctyl(meth)acrylate, n-nonyl(meth)acrylate, iso-nonyl(meth)acrylate,decyl(meth)acrylate, isodecyl acrylate, isodecyl methacrylate,dodecyl(meth)acrylate, isobornyl(meth)acrylate, hydroxyethylmethacrylate, hydroxyethyl acrylate, allyl methacrylate, cyclohexylmethacrylate, cyclohexyl acrylate, n-hexyl acrylate, n-hexylmethacrylate, isobornyl acrylate, isobornyl methacrylate, and the like.Most preferably, the acrylate monomers are acrylic acid and 2-ethylhexylacrylate.

Functionality can be built in to the tackifier resin by choosing anacrylate monomer containing at least one functional group. Thefunctional group can be selected from hydroxy, cycloaliphatic, acid,epoxide, amide, acrylonitril and acrylate groups. Most preferable, theacrylate monomer contains acid groups or hydroxyl groups. Thisfunctionality can lead to even better cohesion in the adhesivecomposition as determined by the Shear Adhesion Failure Test (SAFT),however, the tackifier resin can be less heat stable due totrans-esterfication reactions. Other specific functional groups can bechosen to improve MVTR, fogging, and adhesion.

The tackifier resin can be produced by any process known in the art. Inone embodiment, the tackifier resin can be produced by a radicalcatalyzed polymerization mechanism:

Decomposition: I - - - 2*R.

Initiation: R.+M - - - M₁.

Propagation: M_(i).+M - - - M_(i+1).

Termination: M_(i).+M_(j). - - - M_(i)+M_(j)

wherein I represents an initiator; R. represents a radical; and Mrepresents a monomer.

Any polymerization initiator known in the art for radical catalyzedpolymerization can be utilized. Initiators are typically chosen based onthe desired molecular weight of the tackifier resin and thepolymerization temperature. The effect of decomposition products of theinitiator on the odor of the tackifier resin can also be a factor.Suitable initiators can be chosen from all kinds of commerciallyavailable organic peroxides, such as, but not limited to, diacylperoxides, dialkylperoxidicarbonates, tert-alkyl peroxyesters,di-tert-alkyl peroxides, tert-alkyl hydroperoxides, ketone peroxides,and mixtures thereof. Preferably, the initiator is selected from thegroup consisting of di-tert-butyl peroxide, dicumyl peroxide, anddi-amyl peroxide.

The radical catalyzed polymerization can occur in a reactor zone in thepresence of at least one solvent. Processes can be utilized without theuse of solvent. Generally, the reactor zone comprises at least onereactor. The solvent can be any solvent that is known in the art to beutilized in radical catalyzed polymerizations. Examples of solventsinclude, but are not limited to, xylene, toluene, ethylbenzene,trimethylbenzene, and mixtures thereof. Preferably, the solvent isxylene or a mixture of the isomers of methyethylbenzene,trimethylbenzene, ethyl-dimethylbenzene, propylmethylbenzene andtetramethylbenzene. Most preferably, the solvent is xylene.

Radical catalyzed polymerization to produce the tackifier resins can bebatch, fed batch or continuous. Reaction temperatures for the radicalcatalyzed polymerization can be from 0 to about 250° C., preferably fromabout 100° C. to about 200° C., and most preferably from 150° C. to 160°C. Initiator levels can be from about 0.1% by weight to about 6% byweight based on the weight of the monomer feed, preferably the amount ofinitiator can range from 0.1% to 3%.

In one embodiment, a process to produce a tackifier resin is providedcomprising contacting a tackifier resin product stream with at least onecarrier at a temperature sufficient to remove a portion of at least oneresidual monomer to produce the tackifier resin. Residual monomer isdefined as unreacted monomer or monomers contained in the tackifierresin. The tackifier resin product stream comprises tackifier resin andoptionally, at least one solvent. A portion of the residual solvent canalso be removed from the tackifier resin product stream. The tackifierresin and solvent were previously discussed in this disclosure.

The tackifier resin concentration is particularly useful in adhesivesfor medical applications since it can have a clear color. The lowresidual monomer concentration in the inventive tackifier resin can alsoreduce or eliminate skin sensitivity properties. It can also give muchbetter fogging behavior of the adhesive composition over adhesivecompositions containing tackifier resins without low residual monomerconcentrations.

The amount of the residual monomer in the tackifier resin depends on theuse of the adhesive composition. In one embodiment, the inventivetackifier resin can have a low residual monomer concentration such thatthe tackifier resin does not significantly decrease the MVTR of theadhesive composition. A tackifier resin does not significantly decreasethe MVTR of the adhesive composition if the MVTR is not decreased bymore than 25%, preferably 10% over the adhesive composition without thetackifier resin. Preferably, the MVTR of the adhesive composition is thesame or increased over the adhesive composition without the tackifierresin. For example, the MVTR of the adhesive composition can range fromabout 200 to about 3000, preferably from 500 to 1500.

The contacting of the tackifier resin product stream with the carrier toremove a portion of the residual monomers can be conducted by any meansknown in the art. Examples of carriers include, but are not limited to,steam, nitrogen and ethane. Preferably, the carrier is stream. Thetemperature and pressure of the carrier is that which is sufficient toremove a portion of the residual monomers to obtain the desired residualmonomer concentration of the tackifier resin or desired MVTR of theadhesive composition. Depending on the application, it may also bedesirous that the residual monomer concentration of the tackifier resinis such that it does not increase fogging of the adhesive composition orcause any significant level of skin sensitivity. Preferably, theresidual monomer concentration of the tackifier resin is less than about600 ppm by weight based on the weight of the tackifier resin, morepreferably less than about 300 ppm by weight, and most preferably, lessthan 250 ppm by weight.

In another embodiment, the residual monomer level of the tackifier resinis less than about 200 ppm aromatic monomer based on the weight of thetackifier resin and less than about 400 ppm acrylic monomer, preferablyless than about 100 ppm by weight aromatic monomer and less than about200 ppm by weight acrylic monomer, and most preferably, less than 100 pmby weight aromatic monomer and less than 150 ppm by weight acrylicmonomer.

In yet another embodiment of this invention, the residual solvent levelin the tackifier resin is less than about 500 ppm by weight based on theweight of the tackifier resin, preferably less than about 200 ppm byweight, and most preferably, less than 50 ppm by weight.

The contacting of the tackifier resin product stream with the carriercan occur at any temperature and pressure sufficient to obtain thedesired residual monomer concentration in the tackifier resin.Preferably, the contacting can occur at a temperature in the range ofabout 150° C. to about 250° C., more preferably, from 160° C. to 220° C.Preferably, the contacting of the tackifier resin product stream withthe carrier occurs at a pressure in the range of about 10 mbar to about1000 mbar, preferably from 20 mbar to 200 mbar.

In another embodiment of this invention, a process to produce thetackifier resin is provided. The process comprises:

a) providing at least one aromatic monomer, at least one acrylatemonomer, and optionally, at least one solvent to a reactor zone toproduce a reaction mixture;

b) polymerizing the reaction mixture in the presence of at least oneinitiator to produce a tackifier resin product stream; and

c) contacting the tackifier resin product stream with a carrier toremove a portion of at least one residual monomer from the tackifierresin product stream to yield the tackifier resin. The process ofcontacting the tackifier resin product stream with the carrier has beenpreviously discussed in this disclosure.

In another embodiment of this invention, a process to produce thetackifier resin is provided. The process comprises:

a) providing at least one aromatic monomer, at least one acrylatemonomer, and optionally at least one solvent to a reactor zone toproduce a reaction mixture;

b) polymerizing the reaction mixture in the presence of at least oneinitiator to produce a tackifier resin product stream;

c) heating the tackifier resin product stream at a temperaturesufficient to remove a portion of at least one residual monomer from thetackifier resin product stream; and

d) contacting the tackifier resin product stream with at least onecarrier to further remove a portion of the residual monomers to producethe tackifier resin. Preferably, the residual monomer concentration ofthe tackifier resin is less than about 600 ppm by weight based on theweight of the tackifier resin. The residual monomer concentration andresidual solvent concentration can vary and were discussed previously inthis disclosure.

The heating of the tackifier resin product stream can be conducted byany method known in the art. For example, the tackifier resin productstream can be heated while in the reactor vessel or it can be removed toother processing equipment. The heating is conducted at a temperatureand pressure sufficient to remove a portion of at least one residualmonomer. The temperature however should not be too high to cause colordeterioration of the tackifier resin. The residual monomer can beremoved by heating the tackifier resin product stream to a temperatureranging from about 150° C. to about 250° C., preferably 160° C. to 220°C. The pressure can vary from about 10 mbar to about 1000 mbar,preferably from 20 mbar to 200 mbar. Generally, the portion removed canrange from about 1% by weight to about 200% by weight based on theweight of the tackifier resin. Preferably, the portion removed can rangefrom 50% by weight to 150% by weight. The duration of the heating variesdepending on the amount of tackifier resin product stream to be handled.For example, the duration can range from about 0.5 hours to about 8hours.

The contacting of the tackifier resin product stream with a carrier waspreviously described in this disclosure.

In another embodiment, a tackifier resin is produced by a processcomprising:

a) providing at least one aromatic monomer, at least one acrylatemonomer, and optionally at least one solvent to a reactor zone toproduce a reaction mixture;

b) polymerizing the reaction mixture in the presence of at least oneinitiator to produce a tackifier resin product stream;

c) heating the tackifier resin product stream at a temperature in arange of about 150° C. to about 250° C. to remove a portion of theresidual monomers from the tackifier resin product stream; and

d) contacting the tackifier resin product stream with a carrier tofurther remove a portion of the residual monomers to yield the tackifierresin having residual monomer concentrations of less than about 200 ppmof aromatic monomer and 400 ppm of acrylate monomer. The residualmonomer level and residual solvent level can vary as discussedpreviously in this disclosure.

In yet another embodiment of the invention, the tackifer resin isproduced by a processs comprising:

a) contacting at least one aromatic monomer, at least one acrylatemonomer, and at least one initiator to produce a monomer-initiatorstream;

b) routing the monomer-initiator stream to a reaction zone containingsolvent at a temperature in the range of about 100° C. to about 250° C.;

c) polymerizing the monomer-initiator feed stream at polymerizationconditions to produce a tackifier resin product stream;

d) optionally, providing an additional amount of initiator to thereaction zone;

e) heating the tackifier resin product stream at a temperature in arange of about 150° C. to about 250° C. and at a pressure of about 10mbar to about 1000 mbar to remove a portion of the residual monomer fromthe tackifier resin product stream; and

f) contacting the tackifier resin product stream with steam at atemperature of about 150° C. to about 250° C. and at a pressure of about10 bar to about 1000 mbar to further remove residual monomers from thetackifier resin product stream to yield the tackifier resin havingresidual monomer concentrations of less than 200 ppm by weight ofaromatic monomer based on the weight of the tackifier resin and 400 ppmof acrylate monomer based on the weight of the tackifier resin. Thetackifier resin can also have a residual solvent concentration of lessthan about 500 ppm.

By careful choice of the type of aromatic monomer and acrylic monomer,it is possible to control and fine-tune the properties of the adhesivecomposition for specific applications. Possible variations in thetackifier resin polymerization process are aromatic monomer type,acrylate monomer type, functionality in the form of acid or hydroxylgroups in the acrylate monomer, different process conditions, which allresult in different softening points and molecular weights of thetackifier resin.

The amount of aromatic monomer repeating units in the tackifier resincan range from about 0.1% to 99.9% based on the total amount of monomerrepeating units in the tackifier resin, preferably from about 20% toabout 70%, and most preferably from 25% to 65%. The amount of acrylatemonomer repeating units in the tackifier resin can range from 0.1% to99.9%, preferably from about 30% to about 80%, and most preferably, from35% to 75% based on the total amount of monomer repeating units in thetackifier resin.

The tackifier resin can have a R&B softening point ranging from being aliquid at room temperature to about 180° C., preferably from about 50°C. to about 150° C., and most preferably, from 75° C. to 120° C. Theacid number of the tackifier resin can range from about 0 to about 300mg KOH/g resin, preferably from about 0 mg KOH/g resin to about 200 mgKOH/g resin, and most preferably from 5 to 150 mg KOH/g resin. Thehydroxyl number can vary from about 0 to about 300, preferably from 0 to200. The MMAP cloud point of the tackifier resin is typically less than50° C., preferably the MMAP ranges from about −20° C. to about 30° C.,and most preferably from −10° C. to 20° C.

The number average molecular weight (Mn) of the tackifier resin canrange from about 1,500 to about 7,000 daltons, preferably from about1,600 to about 4,500, and most preferably from 2,000 to 4,000. Theweight average molecular weight (Mw) of the tackifier resin can rangefrom about 2,000 to about 25,000 daltons, preferably from about 2,500 toabout 12,000 and most preferably from 3,000 to 10,000. The z-averagemolecular weight (Mz) of the tackifier resin can range from about 3,000to about 75,000 daltons, preferably from about 4,500 to about 30,000,and most preferably 5,000 to 20,000.

In one embodiment of this invention, the Gardner color of the tackifierresin generally is lower than 5, preferably is lower than 2, and mostpreferably is lower than 1. When the tackifier resin is used in medicalapplications, the Gardner color of the tackifier resin is generallylower than 2, and preferably is lower than 1. Light colored tackifierresins are often required for certain applications, especially in themedical adhesive field.

When the adhesive composition is used in medical applications, theresidual monomer concentrations in the tackifier resin is typically lessthan about 200 ppm by weight aromatic monomer based on the weight of thetackifier resin and less than about 400 ppm by weight acrylic monomerbased on the weight of the tackifier resin. Preferably, the amount ofresidual aromatic monomer is less than about 100 ppm by weight, and theamount of residual acrylic monomer is less than about 200 ppm by weightbased on the weight of the tackifier resin. Most preferably, the amountof residual aromatic monomer is less than 100 ppm by weight based on theweight of the tackifier resin, and the amount of residual acrylicmonomer is less than 150 ppm based on the weight of the tackifier resin.

Also, especially for use in medical applications, the residual solventin the tackifier resin is less than about 500 ppm based on the weight ofthe tackifier resin, preferably less than about 200 ppm, and mostpreferably, less than 50 ppm.

In another embodiment of this invention, the tackifier resin comprisesmonomer repeating units from at least one aromatic monomer and monomerrepeating units from at least one acrylate monomer, wherein the monomerrepeating units is at least one selected from styrene, acrylic acid, and2-ethylhexyl acrylate. The amount of styrene repeating units can rangefrom 0.1 to 99.9% based on the total amount of monomer repeating unitsin the tackifier resin. The amount of acrylic acid and 2-ethylhexylacrylate can range from 0.1% to 99.9% based on the total amount ofmonomer repeating units in the tackifier resin. Preferably, the amountof styrene repeating units can range from about 20% to about 70%, andthe combined amount of acrylic acid repeating units and 2-ethylhexylacrylate repeating units can range from about 30% to about 80%. Mostpreferably, the amount of styrene repeating units can range from 25% to65%, and the combined amount of acrylic acid repeating units and2-ethylhexyl acrylate repeating units can range from 35% to 75%.

When polymerization occurs at a temperature lower than about 160° C.,the amount of acrylic acid in the tackifier resin can be less than about30% in order to help prevent gelling of the tackifier resin. However, atpolymerization temperatures in the range of about 160° C. to about 250°C., the amount of acrylic acid in the tackifier resin can range from0.1% to 99.9%.

Any acrylic polymer can be utilized that is compatible with thetackifier resin. Acrylic polymers include both homopolymers, copolymers,and terpolymers. The copolymers can be random, block or graft. Theacrylic polymers can comprise repeating units from at least one acrylicmonomer listed previously in this specification for tackifier resins.

Acrylic polymers can be produced by copolymerizing acrylic monomers withpolar copolymerizable monomers. Examples of such polar copolymerizablemonomers include, but are not limited to, cyanoalkyl acrylates,acrylamides, or substituted acrylamides, N-vinyl pyrrolidone, N-vinylcaprolactam, acrylonitrile, vinyl chloride, vinylidene chloride, diallylphthalate, and the like. When polar copolymerizable monomers areutilized, the amount of the polar copolymerizable monomer ranges from 0to about 50% by weight based on the weight of the acrylic polymer,preferably from 0 to 30% by weight.

Examples of acrylic polymers include, but are not limited to, acryliccopolymers, acrylated polyethers, acrylated polyester-basedpolyurethanes, methacrylated polyesters, and acrylated epoxies.

Examples of commercially available acrylic polymers include, but are notlimited to Solucryl 300 and Solucryl 303 solvent-based acrylic polymersproduced by UCB in Brussels, Belgium and Acronal® V215 water-basedacrylic polymer produced by BASF.

In one embodiment of this invention, the acrylic polymer can be producedduring the polymerization process of the tackifier resin. For example,acrylic monomers and oligomers can be added during a radical catalyzedpolymerization to produce the tackifier resin. The acrylic monomers andoligomers can be added in the reactor zone of a radical catalyzedpolymerization process as a single type of monomer or oligomer or as amixture and can be added in varying amounts and at varying additiontimes during the polymerization.

Any acrylic monomers known in the art can be utilized that produceacrylic polymers that are compatible with the tackifier resin. In oneembodiment, the acrylic monomers utilized can be at least one from theacrylic monomers listed previously in this specification for tackifierresins. Preferably, the acrylic monomer is at least one selected fromthe group consisting of acrylic acid, 2-ethylhexyl acrylate, methylmethacrylate, methyl acrylate, acrylic acid, methacrylic acid, methylmethacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butylmethacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexylacrylate, n-hexyl methacrylate, ethylhexyl acrylate, ethylhexylmethacrylate, n-heptyl acrylate, n-heptyl methacrylate,2-methylheptyl(meth)acrylate, octyl acrylate, octyl methacrylate,isooctyl (meth)acrylate, n-nonyl(meth)acrylate, iso-nonyl(meth)acrylate,decyl(meth)acrylate, isodecyl acrylate, isodecyl methacrylate,dodecyl(meth)acrylate, isobornyl(meth)acrylate, hydroxyethylmethacrylate, hydroxyethyl acrylate, allyl methacrylate, cyclohexylmethacrylate, cyclohexyl acrylate, n-hexyl acrylate, n-hexylmethacrylate, isobornyl acrylate, isobornyl methacrylate, and the like.

Any acrylic oligomers known in the art can be utilized that producedacrylic polymers that are compatible with the tackifier resin. In oneembodiment, the acrylic oligomers can comprise repeating units from atleast one acrylic monomer listed previously in this specification fortackifier resins. Preferably, the acrylic oligomers comprise at leastone repeating unit selected from the group consisting of acrylic acid,2-ethylhexyl acrylate, methyl methacrylate, methyl acrylate, acrylicacid, methacrylic acid, methyl methacrylate, ethyl acrylate, ethylmethacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate,isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate,ethylhexyl acrylate, ethylhexyl methacrylate, n-heptyl acrylate,n-heptyl methacrylate, 2-methylheptyl(meth)acrylate, octyl acrylate,octyl methacrylate, isooctyl(meth)acrylate, n-nonyl(meth)acrylate,iso-nonyl(meth)acrylate, decyl(meth)acrylate, isodecyl acrylate,isodecyl methacrylate, dodecyl(meth)acrylate, isobornyl(meth)acrylate,hydroxyethyl methacrylate, hydroxyethyl acrylate, allyl methacrylate,cyclohexyl methacrylate, cyclohexyl acrylate, n-hexyl acrylate, n-hexylmethacrylate, isobornyl acrylate, isobornyl methacrylate, and the like.

The amounts of tackifier resin and acrylic polymer in the adhesivecomposition various depending on the properties of the adhesivecomposition desired. In one embodiment of this invention, the amount oftackifier resin ranges from about 0% to about 50% based on the weight ofthe adhesive composition, preferably 0% to 25%.

The composition of the adhesive composition may be adjusted by adding asurfactant or by diluting with water or an aqueous medium. In addition,various additives can be added to the adhesive composition to give theadhesive composition desired properties or for preventing degradation,or for any other purpose. Such additives include, but are not limitedto, reinforcing agents, fire retardants, foaming agents, conventionaltackifiers, plasticizers, oils, antioxidants, polymers, curable/reactivemonomers, crosslinking agents, fillers, and pigments. Because of thenumber of possible compounding ingredients, the properties of theadhesive composition prepared according to this invention can be variedto satisfy most foreseeable requirements for tack, peel, strength, shearstrength, and solvent media resistant, on whatever combination ofsubstrate utilized.

In another embodiment of this invention, a process is provided toproduce the adhesive composition. The process comprises contacting atleast one tackifier resin and at least one acrylic polymer to producethe adhesive composition. The tackifier resin and acrylic polymer werepreviously described in this disclosure.

In another embodiment of this invention, a process is provided toproduce an adhesive film. The process comprises: 1) providing at leastone tackifier resin and at least one acrylic polymer to produce anadhesive composition, and 2) contacting the adhesive composition with atleast one substrate.

Variations of properties of a given adhesive composition can be obtainedby varying the process conditions. For example, properties can bechanged by the selection of substrate, by curing in air or an inertatmosphere, and by varying the intensity of the radiation.

The adhesive composition can be coated on a substrate by any methodknown in the art. For example, the coating can be accomplished by knifecoating, roll coating, gravure coating, and curtain coating. Coatingthickness varies depending on the application. Suitable coatingthicknesses are in the range of about 0 g/m² to about 200 g/m²,preferably, from 10 g/m² to 100 g/m².

The adhesive composition can be coated on a wide array of substrates.Suitable examples include, but are not limited to, polymer films such aspolyethylene terephthalate (PET) and biaxially oriented polypropylene(BOPP); woven and non-woven fabrics; metals and metal foils, such asaluminum copper lead, gold and the like; paper; glass; ceramics; andcomposite materials comprising laminates of one or more of thesematerials.

Possible adhesive applications in which the adhesive composition may beused are numerous. Examples include, but are not limited to,skin-contact medical applications, surgical tapes, bandages, wound care,operation tapes and drapes, hygiene applications including feminine careproducts, box sealing tapes, masking applications, low fogging,automotive interior applications including foam gaskets, instrumentdisplays, sound deadening, trim bonding, sealants, chaulks, generalpressure sensitive adhesives, semi-pressure sensitive adhesives,building & hydroxyl ion adhesives, assembly adhesives, adhesive filmsand membranes, bottle labeling, water soluble adhesives, laminatingadhesives, adhesives for flexible packaging, concrete curing compounds,mounting tapes, double sided tapes, electrical tapes, permanent andremovable labels, filmic labels, pressure sensitive adhesives for thegraphic industry, labels for laser printers, insulation tapes, primercompounds, tie layers, road marking adhesives, inks, mounting tapes,labels for chemicals (sea water resistance), and labeling forpharmaceuticals and cosmetics, etc.

Another embodiment of this invention comprises a laminated structure ofat least a first and a second substrate, the substrates being joined bya layer of the adhesive composition.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

EXAMPLES

This invention can be further illustrated by the following examples ofpreferred embodiments thereof, although it will be understood that theseexamples are included merely for purposes of illustration and are notintended to limit the scope of the invention unless otherwisespecifically indicated.

Test Methods

Acid number was determined by ASTM D974-02.

Compatibility of the tackifier resin was determined by mixing thetackifier resin with an adhesive component in the desired ratio at about150° C. to produce a tackifier resin/adhesive component mixture. Thetackifier resin/adhesive component mixture was then poured on a heatbank. The heat bank consisted of a metal plate with a temperaturegradient from 50° C. to 200° C. On the left side, the heat bank wascool, on the right side, the heat bank was warm, and in between thesetwo points, a temperature gradient was calibrated. A clear tackifierresin/adhesive component mixture indicated a compatible system. Hazytackifier resin/adhesive component mixtures were incompatible. When thetackifier resin/adhesive component mixture stayed clear over the entireheat bank, the cloud point or compatibility temperature was <50° C. Whenthe tackifier resin/adhesive component mixture was cloudy over theentire bank, the cloud point was >200° C. When the tackifierresin/adhesive component mixture was clear above a certain temperatureand cloudy below a certain temperature, the temperature at which it wascloudy was the cloud point. Table 1 below summarizes the results of thistest:

TABLE 1 Compatibility Test Compatibility Temperature ResultsCompatibility temperature <50° C. Completely compatible system 100° C. >compatibility temperature >50° C. Reasonable compatible system 150° C. >compatibility temperature >100° C. Partly compatible systemCompatibility temperature >150° C. Incompatible system

Fogging was determined by ASTM D5393-97.

Gardner Color was measured using ASTM D1544-98.

Hydroxy number was measured using ASTM D464.

Loop tack was determined according to the European Association For SelfAdhesive Tape Industry (AFERA) method 4015.

Lymph Node Assay was conducted accorded to the Organisation for EconomicCo-operation and Development (OECD) draft new guideline 429: SkinSensitization: Local Lymph Node Assay (LLNA) and according to the OECDPrinciples of Good Laboratory Practice (as revised in 1997), Paris,ENV/MC/CHEM(98)17.

Three deviations were made in the LLNA. First, the mice were marked foridentification differently. Secondly, the protocol calls for CO₂/NO₂anesthesia at autopsy, however, due to practical reasons, the mice weresacrificed by using euthasate. Thirdly, instead of analysis of(co)variance followed by Dunnett's multiple comparison tests,statistical analyses were performed by means of the Welch-ANOVA (for³H-thymidine incorporation in the auricular lymph nodes (ARN)) becauseLevene's test for variances showed that variances occurred between thedifferent groups.

Mettler Drop Softening Point (MDSP) was determined by a modified ASTMD6090-99 method. The method was modified in that the measurement wasperformed without a ball and using a cup with a 4.5 mm hole.

MMAP Cloud Point (methylcyclohexane and aniline) was determined by ASTMD-611.

Molecular weight distribution parameters, Mn, Mw, Mz and Mp (weight atthe top of the peak) were determined by Gel Permeation Chromatography(GPC) on a Waters GPC 2690 system equipped with Waters Styragel HR2(7.8×300mm) columns and a Waters 410 RI detector. Polystyrene standardswere used for calibration.

Moisture Vapor Transport Rate (MVTR) was measured by ASTM 3-96.

Peel was determined by AFERA 4001. The following definitions areutilized to interpret the data from this test. Cohesive failure andslip-stick are defined in the Handbook of Pressure Sensitive AdhesiveTechnology, 2nd Edition, edited by Don Satas and Van Nostrand Reinhold.Cohesive failure is a failure mode leaving adhesive residue on the testpanel. Slip-stick is a failure mode in which the peel force is notsmooth but starts to fluctuate periodically from low to high force.

Residual monomer levels were determined by a gas chromatograph (GC) forthe styrene, 2-ethylhexyl acrylate and xylene and with a highperformance liquid chromatograph (HPLC) for acrylic acid.

The procedure followed when using the gas chromatograph is describedbelow. About 5 grams of the sample and 50 mg anisole were placed in aflask, and 10 ml of acetronitrile were added. Then, the sample wasdissolved in an ultrasound bath. A Trace 2000 GC Thermo Quest wasutilized having a CP-WAX 57 CB (Chrompack) column having a length of 25meters, an inner diameter of 0.25 mm, and a film thickness of 0.2 um.The temperature was 50° C. for 20 minutes with a change of temperatureof 4° C. per minute, and a maximum of 200° C. was achieved for 5minutes. The detector was a FID at 230° C. A split injector wasutilized, and the carrier was hydrogen. The internal standard utilizedwas 250 mg anisole, and 50 mg of the substance to be analyzed (e.g.xylene, acrylate) were dissolved in 10 ml of acetonitrite.

The procedure followed when using HPLC is described below. This methodwas used for the analysis of styrene-acrylate tackifier resins todetermine the residual acrylic acid content. The samples were dissolvedin tetrahydrofuran or carbon disulfide and then filtered prior toanalysis by reverse phase HPLC. An external standard of acrylic acid wasused for calibration. The acrylic acid standard and the styrene-acrylatetackifier resin samples were analyzed on a Zorbax® RX-C18 column (5μm),using a two-part gradient. This two-part gradient consisted of part (1)2% methanol in 0.05 M phosphoric acid for the elution of the acrylicacid and part (2) 100% tetrahydrofuran for purging the column during theactual sample analysis. The purge helped to minimize chromatographicproblems for repetitive analysis. Peak detection was accomplished bymonitoring the eluent with a UV detector. The primary UV wavelengthmonitored was 200 nm. The average response factor for acrylic acid wasdetermined by several injections. The calibration curve of the acrylicacid standard was linear over the range of 0–1000 ppm with a lower limitof detection of about 5 ppm.

The following is a summary of the apparatus and chromatographicconditions utilized for the HPLC.

Apparatus:

(1) Liquid chromatograph, Hewlett-Packard Model 1090, or equivalent.

(2) Ultraviolet (UV) detector, Hewlett-Packard Model 1100, orequivalent.

(3) Data system or integrator capable of measuring peak area.

(4) Column, Zorbax® RX-C18 (5 μm), 150 mm×4.6 mm—available from Agilentlocated in Palo Alto, Calif.

(5) Guard column cartridge, Zorbax® RX-C18 (5 μm), 12.5 mm×4.6mm—available from Agilent, or equivalent.

(6) Sample loop injection valve, 5 μL, Rheodyne Model 7125—availablefrom Supelco located in Bellefonte, Pa.

(7) Vortex mixer—available from VWR Scientific located in West Chester,Pa.

Chromatographic Conditions

Flow rate: 1.0 ml/min Injection volume: 5 μL Column oven temperature:40° C. Detector: UV Wavelengths: 200 nm, 210 nm Mobile Phase: A =Methanol/5 mmol H₃PO₄ in water (2/98) B = Tetrahydrofuran (100)Gradient: Part 1) 0–10.10 min 100% A Part 2) 10.10–25.0 min 100% B(column purge)

Ring and Ball Softening Point was determined by ASTM E-28 with WalterHerzog MC-753 equipment.

Shear Adhesion Failure Test (SAFT) was determined when tape was placedon a metal plate weighing 1 kg. The tape on this plate was heated from30° C. with the heat increasing by 0.37° C./minute until the tapereleased from the plate.

Shear was determined by AFERA 4012.

UV absorbance was measured spectrophotometrically using a DR/4000 USpectrophotometer supplied by Lange Group in Tiel, The Netherlands.

UV-C is the effective wavelength for curing a UV-curable adhesivecomposition. UV-C was measured with a calibrated UVICURE PLUS 8788, aself-contained electro-optic radiometer obtained from ElectronicInstrumentation and Technology, Inc, Sterling, Va.

In some experiments, the total UV dose was measured. In others, the UV-Cdose was measured. A relation between total UV dose and UV-C dose wasdetermined for the equipment utilized in these examples. Testing wasconducted by varying the UV dose for some UV-curable adhesivecompositions. The results are given in FIG. 1 and Table 2

TABLE 2 Relation Between Total UV Dose and UV-C Dose for the EquipmentUsed UV total UV-C 139 18 195 26 311 42 470 64Table 2 and FIG. 1 can be used to compare the results when measuringtotal UV rather than UV-C.

Inventive Example 1 Synthesis of the Inventive Styrene-AcrylateTackifier Resins

Styrene-acrylate tackifier resins were produced in a high-pressurereactor using a fed batch method. Xylene was used as a solvent and waspumped into the reactor and heated with stirring under nitrogenatmosphere to 150° C. The monomers (styrene, acrylic acid, and 2-ethylhexyl acrylate) and 2% by weight initiator based on the weight of themonomers were mixed to produce a monomer-initiator feed stream. Themonomer-initiator feed stream was added gradually to the hot solventover two hours to produce a reaction mixture. During the addition of themonomer-initiator feed, the reaction temperature was maintained at 150°C.

After the monomer-initiator feed stream addition was completed, thereaction mixture was stirred for another 30 minutes at this temperatureand at a pressure of about 3 bar. Subsequently, a small amount ofinitiator was post-added, and the process was maintained for another 30minutes at 150° C. to produce a tackifier resin product stream. Thestyrene-acrylate tackifier resin was isolated from the tackifier resinproduct stream by distilling off the solvent. The temperature was slowlyincreased to 170° C., and vacuum was applied up to 25 mbar. After about30 minutes, 90% of the solvent was evaporated. After 2.5 hours, thetemperature reached 170° C. and vacuum reached 25 mbar, and about 99% ofthe solvent was removed. At this point, steam from the bottom of thereactor was injected resulting in about 0.5 liter of condensate perminute. Vacuum was slightly increased to 40 mbars as a result of thesteam stripping. Steam stripping of the styrene-acrylic tackifier resinoccurred for about 9 hours for Formulation I and 7 hours for FormulationII. The properties of the styrene-acrylate tackifier resin produced inthis process are given in Table 3.

TABLE 3 Tackifier Resin Formulations and Properties Styrene-Acrylic DataStyrene-Acrylic Data Tackifier before Tackifier before Formulation Isteaming Formulation II steaming Styrene (wt %) 61.2 24.9 2-Ethylhexyl30.7 44.2 acrylate (wt %) Acrylic acid 8.0 13.7 (wt %) DTBP¹ (wt % 1.71.5 based on total monomer weight) Temperature 153 150 (° C.) R&BSoftening 99.7 98.3 82.1 Point (° C.) Color, Gardner 0.1 0.1 0.5 AcidNumber, 60.1 59.1 112 mg KOH/g Mz, Daltons 15060 13400 Residuals:Styrene, ppm 29 34 <10 20 2-ethylhexyl 12 476 40 990 acrylate, ppmAcrylic Acid, 110 218 134 ppm Solvent, ppm 24 1092 <10 640 ¹DTBP—di-tertbutyl peroxide

Residual styrene levels were less than 29 ppm, and residual 2-ethylhexylacrylate levels were less than 40 ppm. Residual acrylic acid was lessthan 134 ppm, and residual solvent was less than 24 ppm. These levelswere significantly less than the residual monomer and solvent levels ofthe styrene-acrylate tackifier resins prior to steaming and to othercommercial tackifiers as shown in Comparative Example 2. It should alsobe noted that the other properties of the styrene-acrylate tackifierresins were hardly effected by removing a substantial portion of theresidual monomers. Low levels of residual monomers are extremelyimportant for the end application, since the residual monomers can causeskin sensitivity. Low residual monomer and solvent levels in thetackifier resins can also positively influence the fogging behavior ofan UV-curable adhesive composition.

Comparative Example 2 Residual Monomer Levels in Other Tackifiers

Tackifier resins were obtained from SC Johnson and evaluated todetermine the amount of residual monomers. The data are shown in Table4.

TABLE 4 Residual Monomer Levels in Comparative Tackifiers Product NameJoncryl 586 Joncryl 678 Joncryl SX815 R&B (° C.) 121.8 165 115.3 AcidNumber 104 216 39 (mg KOH/g) Gardner Color 0 0 0 MMAP (° C.) 35 57 42 Mp(Daltons) 4161 8064 10285 Mn (Daltons) 2692 4621 5455 Mw (Daltons) 49219663 11275 Mz (Daltons) 8432 17755 19550 Residual Monomer Acrylic Acid585 2200 580 (ppm) Styrene (ppm) 1200 200 60 Alpha-methyl 1000 800–900600 styrene (ppm)

As can be observed from the data in Table 4, the residual monomerconcentration for the tackifier resins from SC Johnson are significantlyabove the inventive tackifier resins.

Example 3 Variation of Monomer Repeating Unit Amounts inStyrene-Acrylate Tackifier Resins—Effect on Properties

The amount of the monomer repeating units in the styrene-acrylatetackifier resins were varied using the same process as described inExample 1, and the resulting properties of the styrene-acrylatetackifier resins were monitored. The results of these experiments aregiven in Table 5.

TABLE 5 Variation of Monomer Amounts in Styrene-Acrylate TackifierResins-Effect on Properties 2-ethyl Acid acrylic hexyl number Exp.styrene acid acrylate MDSP Colour mg MMAP Mp Mn Mw Mz No wt % wt % wt %° C. Gardner KOH/g ° C. Dalton Dalton Dalton Dalton 3.1 25 5 70 44.9 0.139 6 7123 3519 8358 15921 3.2 25 15 60 84.4 0.4 112 7 8462 3729 1013921198 3.3 25 25 50 114.9 0.6 187 15 7725 3390 9382 18976 3.4 38.3 11.750 95.9 0.2 88 4 10100 4099 11752 23766 3.5 38.3 18.3 43.3 112.9 0.3 13016 10916 3859 12729 27459 3.6 45 5 50 76.2 0.3 35 −2 11030 4434 1229923896 3.7 45 25 30 141.2 0.7 172 32 12128 4087 18170 52090 3.8 51.7 11.736.7 116.4 0.2 87 15 12560 4712 14004 27649 3.9 55 20 25 142.7 0.5 14131 12418 3953 14815 32181 3.10 65 5 30 108.5 0.2 37 11 12712 5138 1395325842 3.11 65 15 20 141.4 0.2 110 27 12997 4405 14603 28915 3.12 65 2510 171.2 1.5 149 44 13415 3831 20018 51019

When the amount of monomer was varied, styrene-acrylate tackifier resinswere obtained with a MDSP from about 44.9° C. to about 171.2° C., withacid numbers from 35 mg KOH/g to 187 mg KOH/g, a MMAP from 4° C. to 32°C., and a Mz from 15921 to 51019 Dalton. More styrene instead of acrylicacid or 2-ethylhexylacrylate made the styrene-acrylate tackifier resinmore aromatic resulting in a higher MDSP and a higher Mz. More acrylicacid increased the acid number and the functionality. It also increasedthe softening point and the MDSP.

Example 4 Skin Sensitivity of the Tackifier Resin

A local lymph node assay test (LLNA) in mice was performed to determineif the styrene-acrylate tackifier of Formulation II in Example 1 hasskin sensitivity properties. Under the experimental conditions, therewere no indications that the styrene-acrylate tackifier resin ofFormulation II (see Example 1) had sensitizing properties.

The basic principle underlying the LLNA is that sensitizers induce aprimary proliferation of lymphocytes in the lymph node draining the siteof chemical application. This proliferation only occurs with allergensand is proportional to the dose applied. Therefore, the LLNA provides asimple means of obtaining an objective, quantitative measurement ofsensitization.

Hexyl cinnamic aldehyde was used as a positive control. The hexylcinnamic aldehyde was mixed in acetone/olive oil to a concentration of25% by volume. A mixture of acetone and olive oil in a 4:1 ratio wasused as a negative control. The tackifier resin was diluted inacetone/olive oil (4:1 v/v) to the desired concentration.

Twenty mice were divided into 5 groups of 4 animals each. Three groupsof 4 mice each were treated with different doses of the tackifier resin(Group B: 10%; Group C: 25%; and Group D: 50%). Group E was treated withthe positive control substance, and Group A was treated with thenegative control. On day 0, 1, and 2, the test substance wasadministered with 25 μl on each ear of the mouse.

The data collected showed that there were no indications that thetackifier resin had skin sensitizing properties.

Example 5 Thermal Stability of Styrene-Acrylate Tackifier Resins

The thermal stability of the styrene-acrylate tackifier resins producedin Example 1 has been studied. The results are given in Table 6. Thestyrene-acrylate tackifier resins were heated as specified in Table 6.

TABLE 6 Thermal Stability of Styrene-Acrylate Tackifier Resins ProducedIn Example 1 Styrene- Styrene Acrylic - Acrylic - Formula I Formula IIR&B softening point Initial 96.3 75.7 (° C.)  3 hours at 160° C. 99.182.9 10 hours at 140° C. 99.2 83.2 Acid number (mg Initial 59 117 KOH/g) 3 hours at 160° C. 59 119 10 hours at 140° C. 59 118 Gardner colorInitial 0.2 0.5  3 hours at 160° C. 0.2 0.7 10 hours at 140° C. 0.3 0.8Molecular weight initial Mn 3804 2970 (Dalton) Mw 9320 7187 Mz 1783314688  3 hours at 160° C. 3671 2928 Mn Mw 9300 7299 Mz 17904 15348 10hours at 140° C. 3718 2979 Mn Mw 9300 7329 Mz 17833 15321

The R&B softening point of the styrene-acrylate tackifier resinincreased slightly upon heating. All other tackifier resin propertieswere not influenced by heating under the given circumstances. Therefore,it can be concluded that the styrene-acrylate tackifier resins do notonly have good gelling stability but also a good heat stability, despitethe fact that no antioxidants were used. The Reactol® AC 11 and AC 18tackifier resins were also aged upon heating, and both products showedan unstable performance. Initially, Reactol® AC11 and AC18 tackifierresins were liquid, after 24 hours at 175° C., the products were gels.This can be due to trans-esterification reactions. However, attemperatures below about 175° C., Reactor® AC11 and AC 18 tackifierresins function well in UV-curable adhesive compositions and do not gel.

Example 6 Moisture Vapor Transfer Rate and Fogging Tests

Two other advantages of the use of styrene-acrylate tackifier resinscompared to conventional tackifiers, such as, Foral® 85-E rosin estersand Kristalex® F100 aromatic resin are that styrene-acrylate tackifierscan give better results in fogging tests and does not significantlyreduce the MVTR of the adhesive composition. Films prepared with an18:85 ratio of tackifier resin to UV-curable acrylic composition wereevaluated. In case of MVTR, the films were transferred to a highlybreathable kimwipe structure, and the values was corrected by assumingthat the resistances (1/MVTR) were additive. Results are given in Table7.

TABLE 7 MVTR Results and Fogging Results of Various Tackifier Resins inacResin ® 258 Acrylic Copolymer (15:85) at a Coating Weight of 30 g/m²and a UV-C Dose of 25 mJ/cm² MVTR Fogging Curing dose 25 25 No resin 97196.5 Foral 85-E 696 81 Kristalex F100 769 83 Styrene-acrylate Tackifier(Formulation 790 95.4 I) Styrene-acrylate Tackifier (Formulation 84396.5 II) Reactol AC 11 1035 78.3 Reactol AC 18 698 88.5 Reactol OS 652478 90.7

Only insignificant decreases in the MVTR was observed for thestyrene-acrylate tackifier resins compared to the acResin® acryliccopolymer alone. In case of Reactol® AC 11 acrylic resin and Reactol® OS65 acrylic resin, even an increase was observed. In case of Reactol® OS65 acrylic resin, the MVTR was even twice as high as for the other filmsso this indicates that the styrene-acrylate chemistry can be modified toeffect MVTR in a controlled way.

The fogging data at 25 mL/cm² clearly showed that the results forstyrene-acrylate tackifiers of Formulation I and II were much betterthan for conventional tackifiers such as Foral® 85-E rosin esters andKristalex® aromatic resin. Foral® 85-E rosin esters and Kristalex®aromatic resins increased fogging while the use of the inventivestyrene-acrylate tackifier resins produced in Example 1 hardly showedany differences in fogging compared to the acResin® 258 acryliccopolymer alone. The Reactol® tackifier resins also tended to increasefogging, which again showed the effect of the residual monomer removal.In case of the styrene-acrylate tackifier resin of Formulation I, almostno increase was observed.

Example 7 Solvent-Based Adhesive Compositions

Styrene acrylate tackifiers can be used to tackify solvent-based acrylicpolymers. These styrene-acrylic tackifier can be used inradiation-curable, heat curable, and non-cured adhesive compositions. Inthis example, two styrene-acrylate tackifier resins, Formulation I andII from Example 1, were compared with two conventional tackifiers in twosolvent-based acrylic polymers, Solucryl 300 and Solucryl 303, producedby UCB in Brussels, Belgium. The tackifier resins were mixed in a 5:85ratio with the solvent-based acrylic polymer and coated at a coatingweight of 30 g/m². The coatings were dried and cross linked for 10minutes at 110° C.

The results were also compared with hot-melt adhesives produced from thestyrene-acrylate tackifier resins of Formulation I and II and acResin®acrylic copolymer produced by BASF. The following procedure was used inthe hotmelt coating method. The acResin® acrylic copolymer and tackifierresin were mixed together in an aluminium tray on a hot-plate at 150° C.to produce a UV-curable acrylic adhesive composition. After the mixing,the UV-curable acrylic adhesive composition was poured in a LC 200pilot-plant-scale Lab-coater and coated onto 200 mm wide bi-axiallyoriented polypropylene (BOPP) film at about an average 7 m/minutecoating speed at 140° C. The coating speed depended on the viscosity ofthe UV-curable adhesive composition, therefore, 7 m/minute was theaverage.

TABLE 8 Application Results of Various Tackifier Resins with acResin ®258 Acrylic Copolymer (15:85) at a Coating Weight of 30 g/m² and a UV-CDose of 50 mJ/cm² Compared with Application Results of Several TackifierResins with Solvent-Based Acrylic Polymers in a Ratio 15:85 at a CoatingWeight of 30 g/m² Peel Adhesion to Peel Adhesion Steel to PE Loop tackto SAFT, 1 kg 1 min 10 min steel 0.5° C./min (N/25 mm) (N/25 mm) (N/25mm) (° C.) Hotmelt, UV Hotmelt, UV Hotmelt, UV Hotmelt, UV acResin ®258, no 6.94 1.01 12.91 141 resin Styrene-acrylic resin 9.09 2.20 16.54100 (Formulation I) + acResin ® 258 Styrene-acrylic resin 11.75 2.5916.38 78 (Formulation II) + acResin ® 258 Solucryl 300, no resin 6.791.37 10.12 155 Styrene-acrylic resin 8.55 1.82 11.28 114 (FormulationI) + Solucryl 300 Styrene-acrylic resin 8.73 1.57 13.22 104 (FormulationII) + Solucryl 300 Reactol AC 11 + Solucryl 6.88 1.25 11.31 151 300Reactol AC 18 + Solucryl 7.83 1.32 12.78 150 300 Foral 85-E + Solucryl8.07 3.05 10.81 144 300 Kristalex F100 * + Solucryl 6.27 1.55 6.42 155300 Solucryl 303, no resin 6.61 2.04 9.02 149 Styrene-acrylic resin 9.221.95 15.15 148 (Formulation I) + Solucryl 303 Styrene-acrylic resin 8.001.39 8.62 79 (Formulation II) + Solucryl 303 Reactol AC 11 + Solucryl7.02 1.46 8.21 148 303 Reactol AC 18 + Solucryl 8.14 1.99 14.94 147 303Foral 85-E + Solucryl 8.46 3.29 8.93 139 303 Kristalex F100 * + Solucryl6.13 1.71 5.46 148 303 * Kristalex F100 was incompatible in the Solucrylpolymers

The results showed that Foral®85-E rosin ester was a very good tackifierfor the Solucryl 300 type. Good peel to PE values were found for Foral®85-E rosin ester, while the SAFT was hardly effected (decreased from155° C. to 144° C.). The use of the styrene-acrylate tackifier resinalso improved peel to steel, to PE and especially loop tack wasimproved, more than with Foral® 85-E rosin ester.

Styrene-acrylate tackifier (Formulation I) was found to be a very goodtackifier for the Solucryl 303® acrylic polymer. Peel to steel and looptack both increased while SAFT was hardly effected. Foral 85-E® rosinester also showed an increase in peel to steel and PE, but the loop tackdecreased, and there was a larger increase in SAFT.

Generally, it can be concluded that depending on the solvent-basedacrylate polymer and the desired properties of the adhesive,styrene-acrylate tackifier resins, such as those of Formulation I and IIin Example 1, can be used as a tackifier resin for solvent-based acrylicpolymers.

When comparing the hotmelt UV-curable adhesive composition to thesolvent-based adhesive compositions, it can be concluded that the use ofthe tackifier resin in hot-melt UV-curable adhesive compositionsgenerally results in lower SAFT values, while SAFT values for thesolvent-based adhesive compositions are higher when using tackifierresins.

Example 8 Water-Based Adhesive Compositions

Styrene-acrylate tackifiers also can be used in water-based acrylicpolymer systems. The tackifier resins were dispersed in water to a 50%dispersion, using a surfactant for stabilization. The final dispersionwas mixed in a 1:3 ratio with Acronal® V215, a water based acrylicpolymer from BASF. The adhesives were coated and dried to 21 gsm.

TABLE 9 Application Results of Various Tackifier Resins in a Water-BasedAdhesive Compositions Containing Acronal ® V215 as an Adhesive ComponentPeel Adhesion to cardboard at Peel Adhesion Loop tack to Shear 23° C. toPE at 23° C. PE at 23° C. adhesion on 5 min 5 min 5 min steel at 23° C.(N/25 mm) (N/25 mm) (N/25 mm) (minutes) Acronal + no resin 7 7 8 8000Styrene-Acrylic Tackifier 4 15 6 2310 (Formulation I) + AcronalStyrene-Acrylic Tackifier 4 14 5 990 (Formulation II) + Acronal ReactolAC 11 + Acronal 10 18 8 195 Tacolyn¹3179H + Acronal 16 25 12 150¹Tacolyn ® 3179H is a rosin ester dispersion produced by EastmanChemical company.

The results in the Table 9 showed that the styrene-acrylate tackifierscan be used in water-based adhesive compositions and show clearly theeffect of the various tackifier resins. The effects appear to besoftening point related. With Reactol AC 11 having the lowest softeningpoint, shear was decreased the most, but peel adhesion clearly increasedcompared to the Acronal® V 215 polymer alone. Using the two othertackifiers, Reactol® AC11 and Tacolyn® 3179H, the shear adhesion wasclearly decreased, and especially peel adhesion to PE was improved. Nolarge differences were found for the adhesion properties betweenstyrene-acrylate tackifier resins of Formulation I and II of Example 1.Only the shear for the styrene-acrylate tackifier resin of Formulation Iwas higher, which was most likely due to the higher softening point. Theproperties of the Reactol® AC 11 acrylic resin came close to theconventional tackifier dispersion (Tacolyn® 3179H), normally used forthese water-based polymers. Adhesion was slightly decreased, butcohesion (shear) was increased.

1. An adhesive composition comprising at least one tackifier resin andat least one acrylic polymer wherein said tackifier resin comprisesmonomer repeating units from at least one aromatic monomer and at leastone acrylate monomer; wherein said tackifier resin has a low residualmonomer concentration, and wherein said residual monomer concentrationof said tackifier resin is less than about 600 ppm by weight based onthe weight of said tackifier resin.
 2. An adhesive composition accordingto claim 1 wherein said aromatic monomer is at least one selected fromthe group consisting of olefinic substituted aromatics.
 3. An adhesivecomposition according to claim 2 wherein said aromatic monomer isselected from the group consisting of styrene, alpha-methyl styrene,vinyl toluene, indene, methylindenes, divinylbenzene, dicyclopentadiene,and methyl-dicyclopentadiene.
 4. An adhesive composition according toclaim 1 wherein said acrylate monomer has the general formula:R₁—CH═CR₂—COOR₃ wherein R₁ is selected from the group consisting ofhydrogen, aliphatic groups, and aromatic groups; wherein R₂ is selectedfrom the group consisting of hydrogen, aliphatic groups, and aromaticgroups; and wherein R₃ is selected from the group consisting ofhydrogen, aliphatic groups, aromatic groups.
 5. An adhesive compositionaccording to claim 4 wherein said aliphatic group has 1 to about 20carbon atoms.
 6. An adhesive composition according to claim 5 whereinsaid aliphatic group has 1 to 12 carbon atoms.
 7. An adhesivecomposition according to claim 4 wherein said aromatic group has about 6to about 20 carbon atoms.
 8. An adhesive composition according to claim4 wherein both R₁ and R₂ of said acrylate monomer are hydrogen.
 9. Anadhesive composition according to claim 1 wherein said acrylate monomeris selected from the group consisting of methyl acrylate, acrylic acid,methacrylic acid, methyl methacrylate, ethyl acrylate, ethylmethacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate,isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate,ethylhexyl acrylate, ethylhexyl methacrylate, n-heptyl acrylate,n-heptyl methacrylate, 2-methylheptyl (meth)acrylate, octyl acrylate,octyl methacrylate, isooctyl (meth)acrylate, n-nonyl(meth)acrylate,iso-nonyl(meth)acrylate, decyl(meth)acrylate, isodecyl acrylate,isodecyl methacrylate, dodecyl(meth)acrylate, isobornyl(meth)acrylate,lauryl methacrylate, lauryl acrylate, tridecyl acrylate, tridecylmethacrylate, stearyl acrylate, stearyl methacrylate, glycidylmethacrylate, alkyl crotonates, vinyl acetate, di-n-butyl maleate,di-octylmaleate, acetoacetoxyethyl methacrylate, acetoacetoxyethylacrylate, acetoacetoxypropyl methacrylate, acetoacetoxypropyl acrylate,diacetone acrylamide, acrylamide, methacrylamide, hydroxyethylmethacrylate, hydroxyethyl acrylate, allyl methacrylate,tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, cyclohexylmethacrylate, cyclohexyl acrylate, n-hexyl acrylate, n-hexylmethacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate,isodecyl methacrylate, isodecyl acrylate, 2-methoxy acrylate, 2-methoxymethacrylate, 2-(2-ethoxyethoxy) ethylacrylate, 2-phenoxyethyl acrylate,2-phenoxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate,caprolactone acrylate, caprolactone methacrylate, polypropyleneglycolmonoacrylate, polypropyleneglycol monomethacrylate,poyethyleneglycol(400) acrylate, polypropyleneglycol(400) methacrylate,benzyl acrylate, benzyl methacrylate, and mixtures thereof.
 10. Anadhesive composition according to claim 1 wherein said acrylate monomerhas up to about 20 carbon atoms.
 11. An adhesive composition accordingto claim 10 wherein said acrylate monomer is selected from the groupconsisting of acrylic acid, 2-ethylhexyl acrylate, methyl methacrylate,methyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate,ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate,isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexylmethacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, n-heptylacrylate, n-heptyl methacrylate, 2-methylheptyl (meth)acrylate, octylacrylate, octyl methacrylate, isooctyl (meth)acrylate,n-nonyl(meth)acrylate, iso-nonyl(meth)acrylate, decyl(meth)acrylate,isodecyl acrylate, isodecyl methacrylate, dodecyl(meth)acrylate,isobornyl(meth)acrylate, hydroxyethyl methacrylate, hydroxyethylacrylate, allyl methacrylate, cyclohexyl methacrylate, cyclohexylacrylate, n-hexyl acrylate, n-hexyl methacrylate, isobornyl acrylate,isobornyl methacrylate, and mixtures thereof.
 12. An adhesivecomposition according to claim 11 wherein said acrylate monomers areacrylic acid and 2-ethylhexyl acrylate.
 13. An adhesive compositionaccording to claim 1 wherein said acrylate monomer contains at least onefunctional group selected from the group consisting of hydroxy,cycloaliphatic, acid, epoxide, amide, acrylonitril and acrylate groups.14. An adhesive composition according to claim 1 wherein said tackifierresin is produced by a radical catalyzed polymerization processutilizing at least one initiator.
 15. An adhesive composition accordingto claim 14 wherein said initiator is selected from the group consistingof diacyl peroxides, dialkylperoxidicarbonates, tert-alkyl peroxyesters,di-tert-alkyl peroxides, tert-alkyl hydroperoxides, ketone peroxides,and mixtures thereof.
 16. An adhesive composition according to claim 1wherein said tackifier resin is produced by a process comprisingcontacting a tackifier resin product stream with at least one carrier ata temperature sufficient to remove a portion of at least one residualmonomer to produce said tackifier resin.
 17. An adhesive compositionaccording to claim 1 wherein said tackifier resin does not significantlydecrease the moisture vapor transport rate of said adhesive compositioncontaining said tackifier resin.
 18. An adhesive composition accordingto claim 17 wherein said tackifier resin does not decrease said moisturevapor transport rate of said adhesive composition by more than 25% oversaid adhesive composition without said tackifier resin.
 19. An adhesivecomposition according to claim 17 wherein said moisture vapor transportrate of said adhesive composition is the same or increased over saidadhesive composition without said tackifier resin.
 20. An adhesivecomposition according to claim 17 wherein said moisture vapor transportrate of said adhesive composition ranges from about 200 to about 3000.21. An adhesive composition according to claim 20 wherein said moisturevapor transport rate of said adhesive composition ranges from about 500to
 1500. 22. An adhesive composition according to claim 1 wherein saidresidual monomer concentration of said tackifier resin is less thanabout 300 ppm by weight based on the weight of said tackifier resin. 23.An adhesive composition according to claim 22 wherein said residualmonomer concentration of said tackifier resin is less than about 200 ppmaromatic monomer based on the weight of said tackifier resin and lessthan about 400 ppm acrylic monomer.
 24. An adhesive compositionaccording to claim 23 wherein said residual monomer concentration ofsaid tackifier resin is less than about 100 ppm by weight aromaticmonomer and less than about 150 ppm by weight acrylic monomer.
 25. Anadhesive composition according to claim 1 wherein said tackifier resinhas a residual solvent concentration less than about 500 ppm by weightbased on the weight of said tackifier resin.
 26. An adhesive compositionaccording to claim 1 wherein the amount of aromatic monomer repeatingunits in said tackifier resin ranges from about 20% to about 70% basedon the total amount of monomer repeating units in said tackifier resin.27. An adhesive composition according to claim 1 wherein the amount ofacrylate monomer repeating units in said tackifier resin ranges fromabout 30% to about 80% based on the total amount of monomer repeatingunits in said tackifier resin.
 28. An adhesive composition according toclaim 1 wherein said tackifier resin has a R&B softening point rangingfrom being a liquid at room temperature to about 180° C.
 29. An adhesivecomposition according to claim 1 wherein the acid number of saidtackifier resin ranges from about 0 to about 300 mg KOH/g resin.
 30. Anadhesive composition according to claim 1 wherein the hydroxyl number ofsaid tackifier resin ranges from about 0 to about
 300. 31. An adhesivecomposition according to claim 1 wherein the MMAP cloud point of saidtackifier resin is less than 50° C.
 32. An adhesive compositionaccording to claim 1 wherein the number average molecular weight (Mn) ofsaid tackifier resin ranges from about 1,500 to about 7,000 daltons. 33.An adhesive composition according to claim 32 wherein said numberaverage molecular weight (Mn) of said tackifier resin ranges from 2,000to 4,000 daltons.
 34. An adhesive composition according to claim 1wherein the weight average molecular weight (Mw) of said tackifier resinranges from about 2,000 to about 25,000 daltons.
 35. An adhesivecomposition according to claim 34 wherein said weight average molecularweight (Mw) of said tackifier resin ranges from 3,000 to 10,000.
 36. Anadhesive composition according to claim 1 wherein the z-averagemolecular weight (Mz) of said tackifier resin ranges from about 3,000 toabout 75,000 daltons.
 37. An adhesive composition according to claim 36wherein said z-average molecular weight (Mz) of said tackifier resinranges from 5,000 to 20,000.
 38. An adhesive composition according toclaim 1 wherein the Gardner color of said tackifier resin is less than5.
 39. An adhesive composition comprising at least one tackifier resinand at least one acrylic polymer wherein said tackifier resin comprisesmonomer repeating units from at least one aromatic monomer and at leastone acrylate monomer; wherein said tackifier resin has a low residualmonomer concentration, and wherein said tackifier resin comprisesmonomer repeating units from styrene, acrylic acid, and 2-ethylhexylacrylate.
 40. An adhesive composition according to claim 39 wherein theamount of styrene repeating units ranges from 0.1% to 99.9% based on thetotal amount of monomer repeating units in said tackifier resin.
 41. Anadhesive composition according to claim 39 wherein the amount of acrylicacid and 2-ethylhexyl acrylate ranges from 0.1% to 99.9% based on thetotal amount of monomer repeating units in said tackifier resin.
 42. Anadhesive composition according to claim 40 wherein the amount of styrenerepeating units ranges from about 20% to about 70% based on the totalamount of monomer repeating units in said tackifier resin, and thecombined amount of acrylic acid repeating units and 2-ethylhexylacrylate repeating units ranges from about 30% to about 80%.
 43. Anadhesive composition according to claim 1 wherein said tackifier resindoes not significantly decrease the moisture vapor transport rate ofsaid adhesive composition comprising said tackifier resin.
 44. Anadhesive composition according to claim 1 wherein said tackifier resindoes not significantly increase fogging of an adhesive compositioncomprising said tackifier resin.
 45. An adhesive composition accordingto claim 1 wherein said tackifier resin does not significantly exhibitskin sensitivity properties.
 46. An adhesive composition according toclaim 1 wherein said tackifier resin does not significantly decrease themoisture vapor transport rate of said adhesive composition comprisingsaid tackifier resin; and wherein said tackifier resin does notsignificantly increase fogging of said adhesive composition.
 47. Anadhesive composition according to claim 46 wherein said tackifier resindoes not significantly exhibit skin sensitivity properties.
 48. Anadhesive composition according to claim 1 wherein said acrylic polymerare selected from homopolymers, copolymers, and terpolymers.
 49. Anadhesive composition according to claim 48 wherein said acrylic polymercomprises at least one acrylate repeating unit selected from the groupconsisting of methyl acrylate, acrylic acid, methacrylic acid, methylmethacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butylmethacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexylacrylate, n-hexyl methacrylate, ethylhexyl acrylate, ethylhexylmethacrylate, n-heptyl acrylate, n-heptyl methacrylate, 2-methylheptyl(meth)acrylate, octyl acrylate, octyl methacrylate, isooctyl(meth)acrylate, n-nonyl(meth)acrylate, iso-nonyl(meth)acrylate,decyl(meth)acrylate, isodecyl acrylate, isodecyl methacrylate,dodecyl(meth)acrylate, isobornyl(meth)acrylate, lauryl methacrylate,lauryl acrylate, tridecyl acrylate, tridecyl methacrylate, stearylacrylate, stearyl methacrylate, glycidyl methacrylate, alkyl crotonates,vinyl acetate, di-n-butyl maleate, di-octylmaleate, acetoacetoxyethylmethacrylate, acetoacetoxyethyl acrylate, acetoacetoxypropylmethacrylate, acetoacetoxypropyl acrylate, diacetone acrylamide,acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxyethylacrylate, allyl methacrylate, tetrahydrofurfuryl methacrylate,tetrahydrofurfuryl acrylate, cyclohexyl methacrylate, cyclohexylacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethoxyethylacrylate, 2-ethoxyethyl methacrylate, isodecyl methacrylate, isodecylacrylate, 2-methoxy acrylate, 2-methoxy methacrylate, 2-(2-ethoxyethoxy)ethylacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate,isobornyl acrylate, isobornyl methacrylate, caprolactone acrylate,caprolactone methacrylate, polypropyleneglycol monoacrylate,polypropyleneglycol monomethacrylate, poyethyleneglycol(400) acrylate,polypropyleneglycol(400) methacrylate, benzyl acrylate, benzylmethacrylate, and mixtures thereof.
 50. An adhesive compositionaccording to claim 48 wherein said acrylic polymer comprises monomerrepeating units from polar copolymerizable monomers.
 51. An adhesivecomposition according to claim 50 wherein said polar copolymerizablemonomers are selected from the group consisting of cyanoalkyl acrylates,acrylamides, or substituted acrylamides, N-vinyl pyrrolidone, N-vinylcaprolactam, acrylonitrile, vinyl chloride, vinylidene chloride, diallylphthalate, and mixtures thereof.
 52. An adhesive composition accordingto claim 1 wherein said acrylic polymer is at least one selected fromthe group consisting of acrylic copolymers, acrylated polyethers,acrylated polyester-based polyurethanes, methacrylated polyesters, andacrylated epoxies.
 53. An adhesive composition according to claim 1wherein said acrylic polymer is produced during the polymerizationprocess of the tackifier resin by the addition of at least one acrylicmonomer or at least one acrylic oligomer to a reactor zone in thepresence of an initiator to produce said tackifier resin and saidacrylic monomer.
 54. An adhesive composition according to claim 53wherein said acrylic monomer is at least one selected from the groupconsisting of methyl acrylate, acrylic acid, methacrylic acid, methylmethacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butylmethacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexylacrylate, n-hexyl methacrylate, ethylhexyl acrylate, ethylhexylmethacrylate, n-heptyl acrylate, n-heptyl methacrylate, 2-methylheptyl(meth)acrylate, octyl acrylate, octyl methacrylate, isooctyl(meth)acrylate, n-nonyl(meth)acrylate, iso-nonyl(meth)acrylate,decyl(meth)acrylate, isodecyl acrylate, isodecyl methacrylate,dodecyl(meth)acrylate, isobornyl(meth)acrylate, lauryl methacrylate,lauryl acrylate, tridecyl acrylate, tridecyl methacrylate, stearylacrylate, stearyl methacrylate, glycidyl methacrylate, alkyl crotonates,vinyl acetate, di-n-butyl maleate, di-octylmaleate, acetoacetoxyethylmethacrylate, acetoacetoxyethyl acrylate, acetoacetoxypropylmethacrylate, acetoacetoxypropyl acrylate, diacetone acrylamide,acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxyethylacrylate, allyl methacrylate, tetrahydrofurfuryl methacrylate,tetrahydrofurfuryl acrylate, cyclohexyl methacrylate, cyclohexylacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethoxyethylacrylate, 2-ethoxyethyl methacrylate, isodecyl methacrylate, isodecylacrylate, 2-methoxy acrylate, 2-methoxy methacrylate, 2-(2-ethoxyethoxy)ethylacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate,isobornyl acrylate, isobornyl methacrylate, caprolactone acrylate,caprolactone methacrylate, polypropyleneglycol monoacrylate,polypropyleneglycol monomethacrylate, poyethyleneglycol(400) acrylate,polypropyleneglycol(400) methacrylate, benzyl acrylate, benzylmethacrylate, and mixtures thereof.
 55. An adhesive compositionaccording to claim 53 wherein said acrylic oligomers comprise repeatingunits from at least one acrylic monomer selected from the groupconsisting of methyl acrylate, acrylic acid, methacrylic acid, methylmethacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butylmethacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexylacrylate, n-hexyl methacrylate, ethylhexyl acrylate, ethylhexylmethacrylate, n-heptyl acrylate, n-heptyl methacrylate,2-methylheptyl(meth)acrylate, octyl acrylate, octyl methacrylate,isooctyl (meth)acrylate, n-nonyl(meth)acrylate, iso-nonyl(meth)acrylate,decyl(meth)acrylate, isodecyl acrylate, isodecyl methacrylate,dodecyl(meth)acrylate, isobornyl(meth)acrylate, lauryl methacrylate,lauryl acrylate, tridecyl acrylate, tridecyl methacrylate, stearylacrylate, stearyl methacrylate, glycidyl methacrylate, alkyl crotonates,vinyl acetate, di-n-butyl maleate, di-octylmaleate, acetoacetoxyethylmethacrylate, acetoacetoxyethyl acrylate, acetoacetoxypropylmethacrylate, acetoacetoxypropyl acrylate, diacetone acrylamide,acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxyethylacrylate, allyl methacrylate, tetrahydrofurfuryl methacrylate,tetrahydrofurfuryl acrylate, cyclohexyl methacrylate, cyclohexylacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethoxyethylacrylate, 2-ethoxyethyl methacrylate, isodecyl methacrylate, isodecylacrylate, 2-methoxy acrylate, 2-methoxy methacrylate, 2-(2-ethoxyethoxy)ethylacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate,isobornyl acrylate, isobornyl methacrylate, caprolactone acrylate,caprolactone methacrylate, polypropyleneglycol monoacrylate,polypropyleneglycol monomethacrylate, poyethyleneglycol(400) acrylate,polypropyleneglycol(400)methacrylate, benzyl acrylate, benzylmethacrylate, and mixtures thereof.
 56. An adhesive compositionaccording to claim 1 wherein the amount of said tackifier resin rangesfrom about 0.1% by weight to about 50% by weight based on the weight ofthe adhesive composition.
 57. An adhesive composition according to claim1 wherein the amount of said tackifier resin ranges from 0.1% by weightto 25% by weight based on the weight of the adhesive composition.
 58. Aprocess of making an adhesive composition, said process comprisingproviding at least one tackifier resin and at least one acrylic polymer;wherein said tackifier resin comprises monomer repeating units from atleast one aromatic monomer and at least one acrylate monomer; whereinsaid tackifier resin has a low residual monomer concentration; andwherein said residual monomer concentration of said tackifier resin isless than about 600 ppm by weight based on the weight of said tackifierresin.
 59. A process according to claim 58 further comprising contactingsaid adhesive composition with at least one substrate to produce anarticle.
 60. A process according to claim 59 wherein said substrate isselected from the group consisting of polyethylene terephthalate,biaxially oriented polypropylene, woven fabrics, non-woven fabrics,metals, metal foils, paper, glass, ceramics, and composite materialscomprising laminates of one or more of these materials.
 61. An adhesivecomposition produced by the process of claim
 59. 62. An adhesivecomposition consisting essentially of at least one tackifier resin andat least one acrylic polymer; wherein said tackifier resin consistsessentially of monomer repeating units from at least one aromaticmonomer and at least one acrylic monomer; wherein said tackifier resinhas a low residual monomer concentration, and wherein said residualmonomer concentration of said tackifier resin is less than about 600 ppmby weight based on the weight of said tackifier resin.
 63. An adhesivecomposition according to claim 62 wherein said aromatic monomer isstyrene.
 64. An adhesive composition consisting essentially of at leastone tackifier resin and at least one acrylic polymer; wherein saidtackifier resin consists essentially of monomer repeating units from atleast one aromatic monomer and at least one acrylic monomer, whereinsaid tackifier resin has a low residual monomer concentration, whereinsaid aromatic monomer is styrene, and wherein said acrylic monomers are2-ethyl hexyl acrylate and acrylic acid.
 65. An article comprising saidadhesive composition of claim
 1. 66. An adhesive composition comprisingat least one tackifier resin and at least one acrylic polymer whereinsaid tackifier resin comprises monomer repeating units from at least onearomatic monomer and at least one other monomer selected from the groupconsisting of sodium 1-allyloxy-2-hydroylpropyl sulfonate andacrylonitrile; wherein said tackifier resin has a residual monomerconcentration less than about 600 ppm by weight based on the weight ofsaid tackifier resin.